Field of the Invention
The invention relates to a method of producing doped polysilicon layers and polysilicon layered structures.
In particular, the invention relates to the fabrication of gate electrodes of transistors and of word lines in microelectronic components. The methods which are usually used for this comprise the successive deposition of four layers, namely gateoxide (SiO2), polycrystalline silicon (generally referred to in short as polysilicon), metal and/or metal silicide and a barrier layer (for example SiO2).
In order to ensure the necessary conductivity, the polysilicon layer is usually doped with doping atoms at high concentrations. In this process, a uniform distribution of the doping atoms over the polysilicon layer is very important. Otherwise, the adhesion of a doped polysilicon layer and adjacent metal (silicide) layer is not sufficient and the highly-doped polysilicon can only be structured with extreme difficulty when the doping level highly fluctuates.
In a particularly frequently used method, the procedure adopted in the context of such layered structures is such that it is only after the structuring of the layered structure by means of an etching procedure that the doping of the polysilicon layer is carried out. The doping atoms are thereby injected into the polysilicon from the adjacent metal silicide layer by heat treatment. It is virtually impossible to achieve uniform distribution of the doping atoms in this way. Another possibility is to add the doping compound to the process gas during the chemical vapor deposition and to deposit the doping atoms together with the silicon. In this way, a more uniform distribution of the doping atoms is attained, but the surface quality and adhesion to adjacent layers is not optimal with the conventional way of carrying out this method.
The adhesion problems between the layers can be eliminated to a certain extent by means of additional cleaning steps before the neighboring layer is applied. Such cleaning steps are however time-consuming and make the fabrication of the semiconductor components more expensive. The quality of the boundary layer (for example changes as a result of oxidization in air) also plays a decisive role in the electrical characteristics.
Difficulties arise with the structuring of the layers owing to different material properties of the individual layers on the one hand, and to concentration fluctuations within a layer on the other hand. It would be desirable to have straight-etched edges over all the layers with the lowest possible degree of damage to the gate oxide as a result of the etching process over the entire surface of the wafer, in order to ensure satisfactory quality of the micro-electronic components. The prior art methods do not fulfill these requirements to a satisfactory degree. On the one hand, the layer thicknesses have to be relatively great owing to the low selectivity of the known etching methods, in order to avoid undercutting of the layers and damage to the gate oxide. For this reason, it is virtually impossible to realize very flat layered structures. The homogeneity of the etching procedure over the area to be etched and the structure of the etched edges are not completely satisfactory either.
Precise structuring of a layered structure requires not only uniform quality of the individual layers within the structure but also a structuring method which runs over a plurality of steps which are selectively adapted to the material properties of the layered structure.
It is accordingly an object of the invention to provide a method of producing doped layers which are mainly composed of polycrystalline silicon which is deposited in a chemical vapor deposition, which overcomes the above-mentioned disadvantages of the heretofore-known devices and methods of this general type and in which the doping material is distributed homogeneously over the entire deposited area and the surface quality and adhesion to an adjacent layer is optimized. It is a further object to provide for processing which is simple and cost-effective and which may be carried out with conventional method steps and devices.
It is again a further object of the invention to provide a method by means of which layered structures which comprise at least one polysilicon layer and in particular one doped polysilicon layer and a metal layer or metal silicide layer can be structured with the highest possible degree of selectivity and homogeneity over the area to be structured, forming etched edges which are as straight as possible over all the etched layers. The selectivity should be high enough to permit the thickness of the layers in the layered structure to be reduced, and thus to permit flat microelectronic components to be fabricated.
With the foregoing and other objects in view there is provided, in accordance with the invention, a method of producing a doped layer primarily composed of polycrystalline silicon, and a method of producing layered structures which include such a doped layer. The method comprises:
forming a polycrystalline silicon layer on a substrate by chemical vapor deposition and doping the layer by adding a doping compound to a process gas during the chemical vapor deposition; and
doping only during a determined deposition period in the forming step and terminating a feed of the doping compound to the process gas while continuing the chemical vapor deposition and forming a layer of substantially undoped silicon as a boundary layer of the doped polysilicon layer.
The novel process makes it possible to fabricate uniformly doped polysilicon layers which can be structured much more easily and better than polysilicon doped in a conventional way. Also, the surface quality and adhesion to an adjacent layer is improved.
With the above objects in view there is also provided a method of structuring a layered structure formed of at least one metal layer or metal silicide layer disposed on a polycrystalline silicon layer, which comprises a three-step process including:
etching with fluorine-containing gas in a first step;
etching with a chlorine-containing gas in a second step; and
etching with a bromine-containing gas in a third step.
Particularly good results can be achieved if both methods are combined with one another to fabricate wafers and semiconductor chips.
Therefore, the invention also relates to wafers and semi-conductor chips produced with one or both methods according to the invention. They are defined as a semiconductor structure, comprising:
a substrate;
a doped polysilicon layer deposited on the substrate and doped in a chemical vapor deposition process;
a substantially undoped boundary layer contiguously formed on the doped polysilicon layer in the chemical vapor deposition process.
In accordance with another mode of the invention, the etching steps comprise etching the metal or metal silicide layer disposed on a boundary layer of substantially undoped silicon disposed on a doped polysilicon layer.
In accordance with an added feature of the invention, the doped polysilicon layer is formed directly on a gate oxide layer.
The doped layers referred to herein are composed mainly of polycrystalline silicon deposited by means of chemical vapor deposition (CVD). These layers are referred to herein in short as doped polysilicon layers for the sake of simplicity.
According to the invention, the layer is doped during its formation by adding the doping compound as a process gas during the chemical vapor deposition of the polycrystalline silicon. In other words, the doping takes place simultaneously with the deposition of the polycrystalline silicon. Compared with the implantation method, special steps for cleaning the polycrystalline silicon before the implantation of the doping atoms and for the implantation of the doping substances themselves are eliminated. As a result, not only can the fabrication time be considerably shortened but also there can be a saving in terms of clean room area. The method according to the invention is thus extremely cost-effective. In addition, it does not require any additional doping devices whatsoever. Furthermore, the in situ doping enables the defect density level and the concentration of impurities to be greatly reduced, which is extremely advantageous in terms of the further processing and also with respect to the reliability of the finished microelectronic component.
In contrast with the conventional CVD doping methods, the method according to the invention is carried out in such a way that the feeding of doping compound to the process gas is terminated toward the end of the method, i.e. after the desired deposition period has expired and the desired concentration of doping atoms has been achieved. As a consequence of this, a boundary layer of undoped polysilicon is deposited on the doped polysilicon. This leads to a considerably better surface quality in comparison with the doped polysilicon being obtained.
This is advantageous for the structuring of the layer and the adhesion to an adjacent layer.
However, the layer composed of undoped polysilicon improves not only the adhesion of the adjacent layer but can also increase the homogeneity of the stoichiometry in the metal silicide layer. This is of particular significance in the boundary surface region of strongly metal-doped polysilicon layers. For example, in the case of tungsten silicide layers with strong tungsten enrichment it has been observed that a stoichiometric equalization occurs during subsequent high-temperature processing steps. Silicon atoms migrate from adjacent regions into the regions which have been strongly enriched with tungsten, and thus give rise to microholes in the adjacent region.
The application of a xe2x80x9ccleanxe2x80x9d, i.e. undoped, polysilicon layer prevents the occurrence of this phenomenon in the boundary surface region and thus ensures that there is a high degree of stoichiometric homogeneity over the entire layer thickness of the metal silicide layer.
Therefore, the deposition of adhesion-promoting layers composed of undoped polysilicon and the production of the doped polysilicon layer can be achieved according to the invention in one operation by suitably setting the concentration of the doping compound in the process gas.
Basically, all atoms of the p-type and n-type which are usual for doping polycrystalline silicon, such as boron, gallium, indium, phosphorus, arsenic, and antimony, are possible as doping atoms. Since the doping atoms are fed to the chemical vapor deposition of the polysilicon in the form of their compounds as a process gas, it is expedient to use compounds which are in gaseous form or which are highly volatile. For example, diborane (B2H6), trimethylboron (B(CH3)3), phosphane (PH3) and arsane (AsH3) are suitable gases.
The doping compounds break down under the process conditions, and the doping atoms are deposited together with the silicon, and are embedded in the polysilicon layer.
The doping compound can be added to the gas stream from the beginning to a proportion which is constant over the entire vapor deposition and which is selected in accordance with the desired ratios of quantities of doping atoms in the polysilicon layer.
In addition, it is possible to keep the ratio of the doping compound and Si-containing compound constant with respect to one another, but to increase the proportion of them in the gas continuously or incrementally in the course of the deposition.
In order to obtain a good thickness homogeneity of the deposited layer over the wafer surface, it may be advantageous to dope with a concentration gradient. A suitable doping profile may be obtained, for example, where the concentration of the doping compound, relative to the overall quantity of fed-in, deposited compounds, is increased in the course of the deposition method.
Advantageously, the deposition of pure silicon is started first, since then the adhesion on the underlying surface is generally better, and then the doping compound is fed in and its concentration increased continuously or incrementally until the desired concentration of doping atoms in the polysilicon is achieved.
On the other hand, it is also possible firstly to add the doping compound to the quantity corresponding to the desired final concentration of doping atoms in the silicon, and to increase the proportion of silicon-containing compound in the gas stream as the vapor deposition progresses.
The method according to the invention can be used to deposit doped polysilicon layers on a wide variety of substrates. The method according to the invention is particularly suitable for fabricating gate electrodes of transistors and word lines of a semiconductor component.
Here, the doped polysilicon layer is deposited, for example, in the manner described above, on the gate oxide layer which is usually composed of silicon dioxide. Subsequently, a layer of metal or metal silicide can be applied to the doped polysilicon layer with the boundary layer made of pure polysilicon. The metal silicide is expediently also applied by means of chemical vapor deposition. It is advantageous in this case that it is possible to employ the same device as that used for depositing the polysilicon layer, but it is expedient to use a different deposition chamber than that for the deposition of the polysilicon. In this way, the fabrication of the gate electrodes and word lines can be carried out particularly simply and economically. All the compounds which are usually used in the case of microelectronic components, and in particular the silicides of cobalt, titanium, tantalum, molybdenum and tungsten, are suitable as metal silicide.
Subsequently, an insulation or barrier layer can also be applied to the metal silicide layer. Here, all the insulation layers which are usually used in microelectronic components are suitable. Insulation layers composed of silicon dioxide and silicon nitride, and here, in particular, so-called TEOS or cap-TEOS layers, which are produced by vapor deposition of tetraethoxysilane are particularly suitable.
Particularly good results in terms of the quality of the layers within the layered structure can be achieved if one or more of the layering steps, and in particular the application of the doped polysilicon layer, can be carried out in a vacuum or high vacuum. It is advantageous if, in particular, the vacuum is maintained when the wafer is transferred from one chamber of the CVD device into the next. For example, the vacuum is therefore expediently not interrupted between the chamber for the polysilicon deposition and that for the metal silicide deposition.
If a layer composed of silicon dioxide or silicon nitride is applied as barrier layer to the layered structure, said barrier layer may serve, in the structuring method according to the invention, as a mask for the etching of the layers lying underneath.
In accordance with an additional feature of the invention, a layered structure with at least one metal layer or metal silicide layer on a layer composed of polycrystalline silicon may be structured.
As already mentioned, the structuring of such layered structures generally presents great difficulties. This is the case if, in particular, the polysilicon layer is a doped layer and, in particular, a layer with doping gradients. It has previously been virtually impossible to structure such layered structures selectively and to form straight etching edges. The method according to the invention remedies this.
As noted, the invention is distinguished by the fact that the etching procedure includes at least three steps, the first step of which uses a fluorine-containing etching gas, the second a chlorine-containing gas, and the third a bromine-containing gas.
In the prior art, two-step etching methods were previously usual for the above-mentioned layered structures.
As a result of the suitable selection of the etching agent and as a result of their being matched to the layers to be structured, extremely selective etching of the individual layers, during which overetching and undercutting can largely be avoided, is successfully carried out.
The etching procedure can be controlled either by selecting a suitable fixed etching period or by determining an end point. In particular a spectroscopic method is suitable for end-point control of one or more of the etching steps. Optical emission spectroscopy (OES), during which the concentration of an etching agent or etching product, which has been determined by means of its emission, provides information on the progress of the etching procedure, is particularly suitable. In this way, the end point of the individual etching steps can be determined very precisely, and precise monitoring of the respective etching processes is ensured.
Furthermore, the residual layer thickness of the layer to be etched can also be ascertained using a spectroscopic method.
In the first step, which can also be referred to as xe2x80x9cbreakthroughxe2x80x9d, a large part of the metal layer or metal silicide layer is etched away with the fluorine-containing etching gas. Only a remainder of the layer, for example approximately 25% of the original layer thickness, is retained. In the subsequent second stepxe2x80x94the main etching step xe2x80x9cmain etchxe2x80x9d, xe2x80x94the residual metal layer or metal silicide layer, and a large part of the polysilicon layer lying underneath, are etched away with chlorine-containing etching gas. The second step is preferably carried out in such a way that a small remainder of the polysilicon layer is retained, for example with a layer thickness of approximately 50 nm. The residual layer thickness of the polysilicon is preferably determined by means of OES. The residual polysilicon is selectively etched away in the third step, the so-called xe2x80x9coveretching stepxe2x80x9d. Bromine-containing etching gas is used for this. The use of the bromine-containing etching gas ensures a high degree of selectivity in this method step and largely prevents the layers lying underneath the polysilicon layer from being attacked. Furthermore, the bromine-containing chemical has the advantage in the overetching step that the metal silicide cannot be undercut. In this way, overetching times of virtually any desired length are possible. This is of great importance in the reduction of transistor dimensions and of the relatively large topography of the underlying surface. This method is particularly suitable if there is a gate oxide layer of silicon dioxide underneath the polysilicon layer. The method according to the invention can therefore be used advantageously on layered structures which comprise layers in the sequence of gate oxide, polysilicon, metal layer or metal silicide layer and barrier layer.
The method according to the invention is suitable for layered structures with a polysilicon layer which may be doped or undoped. Particularly good results are achieved if, in the case of a doped polysilicon layer, the doping takes place in accordance with the doping method described at the beginning. The layered structures fabricated according to the method explained above are particularly well suited to structuring according to the structuring method in accordance with the invention. Because of the high degree of selectivity of the structuring method according to the invention and the excellent homogeneity over the entire area of the layers to be structured, it is possible to reduce the thickness of the individual layers in the layered structure without overetching of the respective layers occurring. This is carried out particularly successfully by means of end-point control of the etching procedure using spectroscopic methods and, in particular, using OES. The avoidance of overetching relates not only to the layers to be structured but also to the layers lying underneath, that is to say to the gate oxide layer, for example. This means that the overall thickness of the layered structure can be significantly reduced. On the one hand, this permits relatively flat microelectronic components to be manufactured and, on the other hand, it is possible to arrange further layers, such as metallization layers or the like over the etched layered structure without exceeding the permissible overall height of a microelectronic component.
The structuring of the layered structure, which comprises at least one metal layer or metal silicide layer on a polysilicon layer, can basically be carried out using the masks usually employed for structuring. For example, the usual resist masks made of photoresistor or the like can be used. However, the structuring is preferably carried out using a hard mask which is applied to the metal layer or metal silicide layer. A mask made of silicon dioxide or silicon nitride is preferably used as hard mask. The silicon dioxide layer can be so-called (Cap)-TEOS, that is to say silicon dioxide, which has been produced from tetraethoxysilane by means of a CVD method. This mask is preferably fabricated from the barrier layer which has been applied as top layer of the layered structure on the metal layer or metal silicide layer. By using such a hard mask, which may be relatively thin, the overall height of the layered structure can be reduced further.
The barrier layer is structured in the usual way. For example, a structured resist mask is initially applied to the barrier layer. Then, the layer is opened with a suitable etching agent. In the case of layers of silicon dioxide or silicon nitride this can be carried out, for example by means of plasma etching with argon, trifluoromethane and oxygen. The structuring of the hard mask is expediently carried out in a different chamber of the etching device from that used for the following three-step or multi-step etching method.
The at least three steps of the etching method for the layers lying underneath the hard mask are preferably carried out in one and the same chamber of the etching device. The etching device can be any of the devices conventionally used for this purpose.
The etching gas used in the first etching step comprises at least one fluorine-containing compound. Preferred fluorine-containing etching gases comprise NF3, SF6, SiF4 or mixtures thereof. Fluorinated hydrocarbons, such as CF4, CHF3 and the like can also be used alone or in a mixture with one or more of the fluorides mentioned above. An etching gas mixture which is preferably used is composed of NF3, HCl, Cl2, He and O2.
A chlorine-containing etching gas is used in the second etching step, which gas can comprise, for example, one or more of the compounds HCl, Cl2 and BCl3. A preferred etching gas is composed of HCl, Cl2, He, and O2.
A bromine-containing gas is used as the etching gas of the third step. Hydrogen bromide serves, for example, as the bromine compound. An etching gas which is composed of HBr, He and O2 is suitable.
In one embodiment, in the third step where a bromine-containing gas is used as the etching gas, a bromine component is essentially the only halogen etching measure.
In another embodiment, in the second step where a chlorine-containing etching gas is used as the etching gas, a chlorine component is essentially the only halogen etching measure.
In another embodiment, in the second step where a chlorine-containing etching gas is used as the etching gas, a chlorine component is substantially the only halogen etching measure.
In another embodiment, in the third step where a bromine-containing gas is used as the etching gas, there is no other halogen element present other than bromine.
The structuring method according to the invention can be used to remove the polysilicon layer, virtually without residue, in the regions which are not protected by the mask, without the underlying layers, that is to say for example the gate oxide layer, being damaged. Traces of impurities or etching residues which may still be present can, if appropriate, be removed by means of a wet-chemical cleaning step adjoining the etching steps. A diluted, aqueous solution of hydrogen fluoride, for example in the ratio of HF to H2O of 1:100 to 200, for example, is suitable for this.
With the structuring method according to the invention, a degree of homogeneity and selectivity which is improved in comparison with the known method is achieved when etching the individual layers in the layered structure. The etching of the layered structure is carried out virtually free of residues and without damage to adjacent layers. The excellent selectivity permits the layers of the layered structure to be made thinner than was previously possible, thus allowing the overall height of microelectronic components to be reduced. In addition, the etching method requires an overall etching time period which is decreased in comparison with the method of the prior art.
Furthermore, straight-etched edges are obtained. This can be achieved particularly advantageously if the wafer to be structured is not held mechanically, but rather electrostatically, in the etching device. Usually, a wafer is mounted in the etching chamber by clamping it mechanically and pressing it onto a seal which is arranged at a particular distance from the cathode of the etching chamber. Between the wafer and the cathode, the thermal contact is produced from a gas, for example helium, under pressure (for example 8 torr). However, in this way the wafer is only secured at the edge and can sag in the inner region, with the result that there are different distances between the edge of the wafer and the cathode, and between the interior of the wafer and the cathode. This leads to non-homogeneous etching results, since the conductance of heat depends both on the pressure of the helium and on the distance between the wafer and cathode.
For this reason, according to the invention the wafer is held electrostatically by setting a specific voltage which, as a rule, lies between 1000 and 1500 V. A gas, generally helium, is passed through channels formed in the cathode, with the result that a type of gas cushion is produced between the cathode and wafer. This way of holding the wafer electrostatically is referred to below as electrostatic chuck. The electrostatic chuck has the effect that straight edges are etched over the entire surface of the wafer. The important factor here is that a uniform distribution of temperature is produced over the entire wafer. In addition, the clamp device which was usual before does not exert any disruptive influences on the plasma in the direct vicinity of the edge of the wafer. Furthermore, a reduction in the particle density can be achieved in this way.
With the above and other objects in view there is also provided, in accordance with the invention, a semiconductor structure, comprising:
a substrate;
a doped polysilicon layer deposited on the substrate and doped in a chemical vapor deposition process;
a substantially undoped boundary layer contiguously formed on the doped polysilicon layer in the chemical vapor deposition process.
In accordance with an additional feature of the invention, a gate oxide layer is disposed underneath the doped polysilicon layer.
In accordance with another feature of the invention, the polysilicon layer has a doping profile starting with substantially pure silicon on a substrate side thereof and merging into doped polysilicon.
In accordance with a concomitant feature of the invention, there is provided a layer of a material selected from the group consisting of metal and metal silicide disposed on the boundary layer. The metal silicide selected from the group of cobalt, titanium, tantalum, molybdenum and tungsten silicide.
Other features which are considered as characteristic for the invention are set forth in the appended claims.
Although the invention is illustrated and described herein as embodied in a method of producing doped polysilicon layers and polysilicon layered structures, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.